Waterborne coating composition

Patent metadata

Field	Value
Publication number	US-12565542-B2
Application number	US-202117916264-A
Country	US
Kind code	B2
Filing date	Apr 2, 2021
Priority date	Apr 9, 2020
Publication date	Mar 3, 2026
Grant date	Mar 3, 2026

Abstract

The present invention generally relates to the field of cross-linkable aqueous vinyl polymer dispersions, to a coating composition comprising said cross-linkable aqueous vinyl polymer dispersions; to a paint formulation comprising said cross-linkable aqueous vinyl polymer dispersions; and to an article coated with the coating composition or the paint formulation. In particular, the present invention provides an aqueous vinyl polymer dispersion PD which comprises the following polymers: —1) an aqueous dispersion of a vinyl polymer P1 obtainable by free radical emulsion polymerization of a monomers mixture comprising: a) 5 to 20 wt % acid functional ethylenically unsaturated monomers M1 or precursors thereof; b) 5 to 25 wt % ethylenically unsaturated monomers M2 containing a polyethylene glycol or monoalkoxy polyethylene glycol moiety; c) up to 90 wt % of non-ionic ethylenically unsaturated monomers M3 other than M1 or M2; d) 0 to 10 wt % ethylenically unsaturated monomers M4 with a functional group for cross-linking after film-formation; e) 0 to 10 wt % of at least one chain transfer agent CTA; where the sum of the wt. % of M1+M2+M3+M4+CTA=100 wt %; —2) an aqueous dispersion or solution of a vinyl polymer P2 obtainable by free radical copolymerization of: a) from 25 to 95 wt % of a ethylenically unsaturated monomers M5 selected from the group of N-vinyl amides with general structure (I) where R 1 and R 2 are alkyl from C 1 to C 5 and may be connected to form a ring-structure, preferably N-vinyl pyrrolidone or N-vinyl caprolactam; b) from 5 to 75 wt % of non-ionic ethylenically unsaturated monomers M3′ other than M5; c) from 0 to 5 wt % of ethylenically unsaturated monomers M4′ with a functional group for cross-linking after film-formation; d) from 0 to 10 wt % acid functional ethylenically unsaturated monomers M1′ or precursors thereof; e) from 0 to 5 wt % of at least one chain transfer agent CTA′; where the sum of the wt. % of: M5+M3′+M4′+M1′+CTA′=100 wt %; —3) a film-forming vinyl polymer P3 under the form of an aqueous dispersion comprising: i) from 20 to 60 wt % of a water-soluble or water dispersible crosslinkable vinyl oligomer OL obtained by emulsion polymerizing a monomer mixture comprising: 1) at least one acid functional ethylenically unsaturated monomer M1″; 2) at least one ethylenically unsaturated monomer M4″ with functionality for crosslinking upon film-formation, other than M1″; 3) at least one ethylenically unsaturated monomer M3″ other than M1″ and M2″, and 5) optionally, at least one chain transfer agent CTA″, and ii) from 40 to 80 wt % of a high molecular weight vinyl polymer P4 prepared by emulsion polymerizing, in the presence of the water-soluble or water-dispersible crosslinkable vinyl oligomer OL, a monomer mixture comprising: 1) optionally one acid functional ethylenically unsaturated monomer M1′″; 2) optionally one or more ethylenically unsaturated monomers M4″′ with functionality for crosslinking upon film-formation, other than M1′″; 3) at least one ethylenically unsaturated monomer M3′″ other than M1′″ and MT′ and 4) optionally, one or more multifunctional ethylenically unsaturated monomers for pre-crosslinking, M5′″, preferably in an amount less than 5 wt %, —Where the total weight of film-forming vinyl polymer P3=wt. % of the water-soluble or water dispersible crosslinkable vinyl oligomer OL+wt. % of the high molecular weight vinyl polymer P4=i)+ii)=100 wt % and—Where the total weight of the vinyl polymer in the aqueous vinyl polymer dispersion PD=wt. % of the vinyl polymer P1+wt. % of the vinyl polymer P2+wt. % of the film-forming vinyl polymer P3=100 wt %.

First claim

The invention claimed is:

1 . An aqueous vinyl polymer dispersion PD which comprises:
1) an aqueous dispersion of a vinyl polymer P1 obtained by free radical emulsion polymerization of a monomers mixture comprising:
a) 5 to 20 wt % acid functional ethylenically unsaturated monomers M1 or precursors thereof;
b) 5 to 25 wt % ethylenically unsaturated monomers M2 containing a polyethylene glycol or monoalkoxy polyethylene glycol moiety;
c) up to 90 wt % of non-ionic ethylenically unsaturated monomers M3 other than M1 or M2;
d) 0 to 10 wt % ethylenically unsaturated monomers M4 with a functional group for cross-linking after film-formation;
e) 0 to 10 wt % of at least one chain transfer agent CTA;
where the sum of the wt. % of M1+M2+M3+M4+CTA=100 wt %;
2) an aqueous dispersion or solution of a vinyl polymer P2 obtained by free radical copolymerization of:
a) from 25 to 95 wt % of a ethylenically unsaturated monomers M5 selected from the group of N-vinyl amides with general structure:

where R 1 and R 2 are alkyl from C 1 to C 5 and may be connected to form a ring-structure;
b) from 5 to 75 wt % of non-ionic ethylenically unsaturated monomers M3′ other than M5
c) from 0 to 5 wt % of ethylenically unsaturated monomers M4′ with a functional group for cross-linking after film-formation
d) from 0 to 10 wt % acid functional ethylenically unsaturated monomers M1′ or precursors thereof;
e) from 0 to 5 wt % of at least one chain transfer agent CTA′;

where the sum of the wt. % of: M5+M3′+M4′+M1′+CTA′=100 wt %;
3) a film-forming vinyl polymer P3 in the form of an aqueous dispersion comprising:
i) from 20 to 60 wt % of a water-soluble or water dispersible crosslinkable vinyl oligomer OL obtained by emulsion polymerizing a monomer mixture comprising:
1) at least one acid functional ethylenically unsaturated monomer M1″;
2) at least one ethylenically unsaturated monomer M4″ with functionality for crosslinking upon film-formation, other than M1″;
3) at least one ethylenically unsaturated monomer M3″ other than M1″ and M2″, and
5) optionally, at least one chain transfer agent CTA″, and

ii) from 40 to 80 wt % of a high molecular weight vinyl polymer P4 prepared by emulsion polymerizing, in the presence of the water-soluble or water-dispersible crosslinkable vinyl oligomer OL, a monomer mixture comprising:
1) optionally one acid functional ethylenically unsaturated monomer M1′″;
2) optionally one or more ethylenically unsaturated monomers M4′″ with functionality for crosslinking upon film-formation, other than M1′″;
3) at least one ethylenically unsaturated monomer M3′″ other than M1′″ and M2′″ and
4) optionally, one or more multifunctional ethylenically unsaturated monomers for pre-crosslinking, M5″′,
wherein the high molecular weight vinyl polymer P4 has a weight average molecular weight of at least 60,000 g/mol,

wherein the total weight of film-forming vinyl polymer P3=wt. % of the water-soluble or water dispersible crosslinkable vinyl oligomer OL+wt. % of the high molecular weight vinyl polymer P4=i)+ii)=100 wt % and
wherein the total weight of the vinyl polymer in the aqueous vinyl polymer dispersion PD=wt. % of the vinyl polymer P1+wt. % of the vinyl polymer P2+wt. % of the film-forming vinyl polymer P3=100 wt %.

2 . The aqueous vinyl dispersion PD according to claim 1 , wherein the weight ratio of the vinyl polymers P1, P2 to P3 is comprised within the range of (1:1:98) to (65:15:20).

3 . The aqueous vinyl polymer dispersion PD according to claim 1 , wherein the vinyl polymer P1 has a number average molecular weight of from 2,000 to 120,000 g/mole as determined by size exclusion chromatography using tetrahydrofuran and 2% acetic acid as eluent and using polystyrene standards, an acid value of from 30 to 150 mg KOH/g as determined by ISO 3682 and from 5 to 25 wt % of ethylenically unsaturated monomers M2 which is selected from the group consisting of a polyethylene oxide and monoalkoxy polyethyleneglycol (meth)acrylates based on the total weight of the vinyl polymer P1.

4 . The aqueous vinyl polymer dispersion PD according to claim 1 , wherein the vinyl polymer P2 has a number average molecular weight Mn from 1,000 to 50,000 g/mole as determined by gel permeation chromatography using hexafluoro-iso-propanol as eluent and using polymethyl methacrylate standards for the calibration curve.

5 . The aqueous vinyl polymer dispersion PD according to claim 1 , wherein the vinyl polymer P2 comprises at least 80% of monomers M3′, the monomers M3′ present in the vinyl polymer P2 having a monomer glass transition temperature Tg lower than 120 °Celsius.

6 . The aqueous vinyl polymer dispersion PD according to claim 1 , wherein the vinyl polymer P2 is a copolymer of N-vinyl pyrrolidone and ethyl acrylate or a copolymer of N-vinyl caprolactam and ethyl acrylate.

7 . The aqueous vinyl polymer dispersion PD according to claim 1 , wherein the water-soluble or water dispersible crosslinkable vinyl oligomer OL has an acid value of at least 45 mg KOH/g.

8 . The aqueous vinyl polymer dispersion PD according to claim 1 , wherein the water-soluble or water dispersible crosslinkable vinyl oligomer OL has a number average molecular weight of from 500 to 50,000 g/mole as determined by size exclusion chromatography using tetrahydrofuran and 2% acetic acid as eluent and using polystyrene standards for the calibration curve.

9 . The aqueous vinyl polymer dispersion PD according to claim 1 , wherein the water-soluble or water dispersible crosslinkable vinyl oligomer OL has a glass transition temperature (Tg) within the range of 10 to 150° C.

10 . The aqueous vinyl polymer dispersion PD according to claim 1 , wherein the high molecular weight vinyl polymer P4 has a glass transition temperature between −70° C. and 50° C. and is at least 25° C. below the glass transition temperature of the water-soluble or water dispersible crosslinkable vinyl oligomer OL.

11 . The aqueous vinyl polymer dispersion PD according to claim 1 , wherein the high molecular weight vinyl polymer P4 has a number average molecular weight that is greater than or equal to 60,000 g/mole.

12 . The aqueous vinyl polymer dispersion PD according to claim 1 , wherein the film-forming vinyl polymer P3 is in the form of an aqueous polymer dispersion and comprises from 20 to 60 wt % of water-soluble or water dispersible crosslinkable vinyl oligomer OL.

13 . The aqueous vinyl polymer dispersion PD according to claim 12 , wherein the aqueous dispersion of vinyl polymer P3 has a solids content within the range of from 20 to 60 wt %.

14 . A coating composition COA comprising the aqueous vinyl polymer dispersion PD according to claim 1 and at least one or more conventional ingredients selected from the group consisting of non-vinyl polymers, pigments, dyes, emulsifiers, surfactants, plasticizers, thickeners, heat stabilizers, levelling agents, anti-cratering agents, fillers, sedimentation inhibitors, UV absorbers, antioxidants, drier salts, organic co-solvents, and wetting agents.

15 . A method of making a coating composition COA according to claim 14 comprising blending the aqueous vinyl polymer dispersion PD with at least one or more conventional ingredients selected from the group consisting of non-vinyl polymers, pigments, dyes, emulsifiers, surfactants, plasticizers, thickeners, heat stabilizers, levelling agents, anti-

Assignees

• Allnex Netherlands Bv
• Allnex Netherlands Bv

Inventors

• Mestach Dirk
• Bohorquez Silfredo
• Akkerman Jaap

Classifications

• C09D133/12

  Homopolymers or copolymers of methyl methacrylate · CPC title

• C08L2205/03

  containing three or more polymers in a blend · CPC title

• C08L2201/54

  Aqueous solutions or dispersions · CPC title

• C08L39/06

  Homopolymers or copolymers of N-vinyl-pyrrolidones · CPC title

• C08L33/12

  Homopolymers or copolymers of methyl methacrylate · CPC title